Droplets distributed in an aqueous medium

ABSTRACT

Provided is a composition comprising droplets distributed in an aqueous medium, wherein the droplets comprise one or more boronic acids, and wherein the aqueous medium comprises polyvinyl alcohol.

Suspensions in aqueous media of liquid droplets of water-insolublecompounds are useful for a variety of purposes. For example, when suchdroplets contain vinyl monomer and initiator, the monomer may undergopolymerization to form polymer particles in a process of suspensionpolymerization. Such polymer particles are useful for a variety ofpurposes, including, for example, as resins that are adsorptive or thatare functionalized to have ion exchange capability or both. Such resinsare used for a wide variety of purposes, including, for example,purification of foods and/or beverages.

In the past, suspensions in aqueous media of liquid droplets ofwater-insoluble vinyl monomers have been stabilized by the addition ofone or more stabilizing compound. One common stabilizing compound isgelatin. Because gelatin is a product derived from animals, manyconsumers do not wish to purchase or consume foods or beverages thatwere processed using methods that included contact with resins that weremade using gelatin. Typically, when gelatin is used, the suspension alsocontains one or more costabilizers. Typical costabilizers arewater-soluble polymers.

U.S. Pat. No. 8,646,907 describes contact lenses in which the lenssurface contains at least one form of boronic acid, boronic ester,boronic anhyhdride, or a combination thereof, present on at least asurface of the lens body, and in which the boronic acid moieties arecomplexed with polyhydric alcohol.

It is desired to provide a method that produces droplets distributed inan aqueous medium, where that method has one or more of the followingbenefits: the method is performed without the use of gelatin or otheranimal products; the method produces a stable suspension of dropletsdistributed in an aqueous medium; the droplets distributed in theaqueous medium are suitable for suspension polymerization; and theresult of performing such an aqueous polymerization is polymer beads ofuniform size distribution.

The following is a statement of the invention.

A first aspect of the present invention is a method of making dropletsdistributed in an aqueous medium comprising bringing into contact

-   -   (i) an organic solution comprising one or more boronic acids,        and    -   (ii) an aqueous solution comprising polyvinyl alcohol

A second aspect of the present invention is a composition comprisingdroplets distributed in an aqueous medium, wherein the droplets compriseone or more boronic acids, and wherein the aqueous medium comprisespolyvinyl alcohol.

A third aspect of the present invention is a method of suspensionpolymerization comprising

-   -   (I) providing a composition comprising droplets distributed in        an aqueous medium, wherein the droplets comprise one or more        boronic acids, one or more monomers, and one or more initiators,        and wherein the aqueous medium comprises polyvinyl alcohol; and    -   (II) stressing the composition so that the initiator initiates        polymerization of the monomer.

The following is a detailed description of the invention.

As used herein, the following terms have the designated definitions,unless the context clearly indicates otherwise.

A spherical particle is characterized by its diameter. If a particle isnot spherical, its diameter is taken to be the diameter of a spherehaving the same volume as the particle.

A composition is considered herein to be a liquid if it is in the liquidstate over a temperature range that includes 15° C. to 40° C.

Ambient conditions herein refer to conditions that normally occur in theenvironment. Ambient conditions include temperature of approximately 23°C. and pressure of approximately 1 atmosphere pressure. Ambientconditions also include conditions in which stressful conditions such asionizing radiation, ultraviolet radiation, reactive chemicals, etc., areeither absent or are present at levels found in the normal environment.

Droplets are discrete particles that contain one or more liquids. Theamount of liquid in the droplet is 80% or more by weight based on theweight of the droplets. A collection of droplets has harmonic mean sizeof 25 μm to 2,000 μm.

An aqueous medium is a liquid that contains 40% or more water by weightbased on the weight of the aqueous medium. Substances dissolved asindividual molecules in the aqueous medium are considered to be part ofthe aqueous medium. Substances that are present as discrete particlesare said to be distributed in an aqueous medium if 50% or more, bycount, of the discrete particles are surrounded by the aqueous medium.Particles that are distributed in an aqueous medium may be in the form,for example, of a suspension, a dispersion, an emulsion, a latex, or acombination thereof. A composition in a container that containsparticles and contains an aqueous medium and that is being subjected tomechanical agitation is considered to have particles distributed in theaqueous medium if the particles meet the above criterion, even ifmechanical agitation is required to prevent the particles from settlingto the bottom of the container, floating to the top of the container,coagulating with each other, agglomerating with each other, or otherwisecoming into a non-distributed configuration.

An organic solution is a liquid that contains 20% or less water byweight based on the weight of the organic medium. An organic solutioncontains 2 or more different chemical compounds. All of the compoundspresent in an organic solution are intimately mixed with each other on amolecular level.

A boronic acid is a compound having structure I:

where R is a chemical group that contains one or more carbon atom. Theboron atom shown in structure I is bonded to a carbon atom in the groupR. Boronic acid may be in the protonated form as shown in structure I orin an anion form, with one or both of the hydrogen atoms shown instructure I removed.

“Resin” as used herein is a synonym for “polymer.” A “polymer,” as usedherein is a relatively large molecule made up of the reaction productsof smaller chemical repeat units. Polymers may have structures that arelinear, branched, star shaped, looped, hyperbranched, crosslinked, or acombination thereof; polymers may have a single type of repeat unit(“homopolymers”) or they may have more than one type of repeat unit(“copolymers”). Copolymers may have the various types of repeat unitsarranged randomly, in sequence, in blocks, in other arrangements, or inany mixture or combination thereof. Polymers have weight-averagemolecular weight of 2,000 or more

Molecules that can react with each other to form the repeat units of apolymer are known herein as “monomers.” The repeat units so formed areknown herein as “polymerized units” of the monomer.

Vinyl monomers have the structure II

where each of R¹, R², R³, and R⁴ is, independently, a hydrogen, ahalogen, an aliphatic group (such as, for example, an alkyl group), asubstituted aliphatic group, an aryl group, a substituted aryl group,another substituted or unsubstituted organic group, or any combinationthereof. Vinyl monomers have molecular weight of less than 1,000. Vinylmonomers include, for example, styrene, substituted styrenes, dienes,ethylene, ethylene derivatives, and mixtures thereof. Ethylenederivatives include, for example, unsubstituted and substituted versionsof the following: vinyl acetate and acrylic monomers. Acrylic monomersare monomers selected from substituted and unsubstituted(meth)acrylonitrile, (meth)acrylic acid, substituted and unsubstitutedalkyl esters of (meth)acrylic acid, substituted and unsubstituted amidesof (meth)acrylic acid, and mixtures thereof. As used herein, the prefix“(meth)acryl-” means either acryl- or methacryl-. “Substituted” meanshaving at least one attached chemical group such as, for example, alkylgroup, alkenyl group, vinyl group, hydroxyl group, alkoxy group,carboxylic acid group, phosphoric acid group, sulfonic acid group, aminogroup, substituted amino group, other functional groups, andcombinations thereof.

As used herein, vinyl aromatic monomers are vinyl monomers in which oneor more of R¹, R², R³, and R⁴ contain one or more aromatic ring.

A monovinyl monomer is a vinyl monomer that has exactly one non-aromaticcarbon-carbon double bond per molecule. A multivinyl monomer is a vinylmonomer that has two or more non-aromatic carbon-carbon double bonds permolecule.

A vinyl polymer is a polymer in which 90% or more of the polymerizedunits, by weight based on the weight of the polymer, are polymerizedunits of one or more vinyl monomers. An acrylic polymer is a vinylpolymer in which 50% or more of the polymerized units, by weight basedon the weight of the polymer, are polymerized units of acrylic monomers.A vinyl aromatic polymer is a polymer in which 50% or more of thepolymerized units, by weight based on the weight of the polymer, arepolymerized units of vinyl aromatic monomer.

Polyvinyl alcohol (PVOH) has the nominal structure III

where n is 100 or more. Also, 0 to 20 mole % of the linkages betweenpolymerized units are in the head-to-tail configuration, which is-[—CH₂—C(X)H—]-[—C(X)H—CH₂—]-, and 80 mole % to 100 mole % of thelinkages between polymerized units are in the head-to-headconfiguration, which is -[—CH₂—C(X)H—]-[—CH₂—C(X)H—]-, where each X is,independently, —OH or —OC(O)CH₃. Typically, PVOH is made bypolymerization of vinyl acetate followed by hydrolysis of 75 mole % to100 mole % of the polymerized units to convert the acetate group to ahydroxyl group.

PVOH is characterized by the parameter “% hydrolyzed,” which is the mole% of the polymerized units that have the composition shown in structureIII, either in the head-to-head configuration or the head-to-tailconfiguration. PVOH is 75% to 100% hydrolyzed. It is considered that thepolymerized units that are not hydrolyzed have the composition—CH₂—C(X)H—, where X is —OC(O)CH₃.

As used herein, an initiator is a molecule that is stable at ambientconditions but that is capable under certain conditions of producing oneor more fragments that bears a free radical, and that fragment iscapable of interacting with a monomer to start a free radicalpolymerization process. The conditions that cause production of afragment bearing a free radical include, for example, elevatedtemperature, participation in an oxidation-reduction reaction, exposureto ultraviolet and/or ionizing radiation, or a combination thereof.

A collection of particles is characterized by the diameters of theparticles. A collection of particles is characterized herein by theparameters D10, D50, and D60. D10 is the value such that exactly 10% ofthe collection of particles by volume have diameter of D10 or less. D50is the value such that exactly 50% of the collection of particles byvolume have diameter of D50 or less. D60 is the value such that exactly60% of the collection of particles by volume have diameter of D60 orless. The parameters D10, D50, and D60 are determined by mixing a sampleof the collection of particles into water to form a dilute slurry andusing laser light scattering to determine D10, D50, and D60.

A collection of particles may also be characterized by the uniformitycoefficient (UC), which is defined herein as UC=D60/D10. Another usefulcharacterization of a collection of particles is “LT355,” which is thepercent by volume of the particles having diameter less than 355 μm.

The harmonic mean size (HMS) of a collection of particles is given bythe formula

${HMS} = {N/{\sum\limits_{i = 1}^{N}\; \left( \frac{1}{d_{i}} \right)}}$

where d_(i) is the diameter of an individual particle, the summationindex i is taken over the individual particles, and N is the number ofparticles.

The present invention involves one or more boronic acids. Preferredboronic acids have structure I shown above where the R group containsone or more aromatic ring. More preferably, the boron atom shown instructure I is bonded to a carbon atom that is a member of an aromaticring in the R group. More preferably, the R group has the structure IV

where R⁵ is an alkyl or alkenyl group; preferably R⁵ has 1 to 6 carbonatoms. More preferably, the R group is phenyl or a substituted phenylgroup. More preferred boronic acids are phenyl boronic acid, butylphenylboronic acid, 4-vinylphenyl boronic acid, and mixtures thereof; morepreferred is 4-vinylphenyl boronic acid.

The boronic acid is dissolved in an organic solution. Preferably,boronic acid is present in the organic solution in an amount, by weightbased on the weight of the organic solution, of 0.002% or more; morepreferably 0.004% or more; more preferably 0.006% or more. Preferably,boronic acid is present in the organic solution in an amount, by weightbased on the weight of the organic solution, of 0.1% or less; morepreferably 0.05% or less; more preferably 0.03% or less; more preferably0.02% or less.

Preferably, the organic solution contains one or more monomers.

Preferred monomers are vinyl monomers. Preferred vinyl monomers arestyrenic monomers, acrylic monomers, and mixtures thereof. Preferably,all the monomers used are selected from vinyl aromatic monomers, acrylicmonomers, and mixtures thereof; more preferably selected from vinylaromatic monomers. More preferably, all the monomers used are selectedfrom vinyl aromatic monomers. Preferably, the vinyl monomer includes oneor more monofunctional vinyl monomer. Preferred monofunctional vinylmonomers are acrylic and styrenic monofunctional monomers; morepreferred are monofunctional styrenic monomers; more preferred isstyrene. Preferably, the vinyl monomer includes one or moremultifunctional vinyl monomer. Preferred multifunctional vinyl monomersare multifunctional styrenic monomers; more preferred is divinylbenzene.

Preferably, little or no vinyl chloride is present. Preferably, theamount of vinyl chloride is, by weight based on the total weight of allmonomers, 0 to 0.1%, more preferably 0 to 0.01%; more preferably 0%.

Preferably, the amount of monovinyl monomer in the organic solution, byweight based on the weight of the organic solution, is 20% or more; morepreferably 50% or more; more preferably 70% or more; more preferably 80%or more; more preferably 84% or more; more preferably 88% or more.Preferably, the amount of monovinyl monomer in the organic solution, byweight based on the weight of the organic solution, is 99.9% or less;more preferably 99% or less; more preferably 98% or less; morepreferably 96% or less; more preferably 94% or less; more preferably 92%or less.

Preferably, the amount of multivinyl monomer in the organic solution, byweight based on the weight of the organic solution, is 0.1% or more;more preferably 0.5% or more; more preferably 1% or more; morepreferably 2% or more; more preferably 4% or more; more preferably 6% ormore; more preferably 8% or more. Preferably, the amount of multivinylmonomer in the organic solution, by weight based on the weight of theorganic solution, is 80% or less; more preferably 50% or less; morepreferably 30% or less; more preferably 25% or less; more preferably 20%or less; more preferably 16% or less; more preferably 12% or less.

The organic solution preferably contains one or more initiators.Preferred initiators have solubility in 100 mL of water at 25° C. of 1gram or less; more preferably 0.5 gram or less; more preferably 0.2 gramor less; more preferably 0.1 gram or less. Preferred are peroxide andhydroperoxide initiators; more preferred are peroxide initiators; morepreferred are benzoyl peroxide and derivatives thereof; more preferredis benzoyl peroxide. Preferably the amount of initiator in the organicsolution is, by weight based on the weight of the organic solution,0.05% or more; more preferably 0.1% or more; more preferably 0.2%.Preferably the amount of initiator in the organic solution is, by weightbased on the weight of the organic solution, 2% or less; more preferably1% or less; more preferably 0.5% or less.

Optionally, the organic solution additionally contains sulfur. Whensulfur is present, the preferred amount of sulfur is, by weight based onthe weight of the organic solution, 0.001% or more. When sulfur ispresent, the preferred amount of sulfur is, by weight based on theweight of the organic solution, 0.02% or less.

The organic solution optionally contains one or more porogens. A porogenis a compound that is liquid at 25° C. and that has solubility in waterat 25° C. of less than 0.5 grams per 100 grams of water. The porogen issoluble (in the amount present in the organic solution) at 25° C. in theorganic solution. When monomer and porogen are both present in theorganic solution, the porogen is preferably chosen so that the polymerthat would be formed by polymerization of the monomer is not soluble inthe porogen. That is, the solubility of such a polymer in the porogen at25° C. is less than 1 gram per 100 grams of porogen. When porogens arepresent, preferred porogens are aliphatic hydrocarbons, aliphaticalcohols, aromatic esters, alkyl fatty acids, and mixtures thereof. Insome embodiments, (herein “porogen rich” embodiments), the amount ofporogen is 10% or more by weight based on the weight of the organicsolution. In porogen rich embodiments, the amount of porogen, by weightbased on the weight of the organic solution, is 10% or more; preferably20% or more; more preferably 30% or more. In porogen rich embodiments,the amount of porogen, by weight based on the weight of the organicsolution, is 60% or less; preferably 50% or less; more preferably 40% orless. In some embodiments (herein “porogen poor” embodiments), theamount of porogen is 5% or less by weight based on the weight of theorganic solution. In porogen poor embodiments, the amount of porogen, byweight based on the weight of the organic solution, is 0 to 5%;preferably 0 to 2%; more preferably 0 to 1%; more preferably 0 to 0.1%;more preferably 0%.

Preferably, all of the ingredients present in the organic solution areintimately mixed with each other on a molecular level. To illustratethis statement, an illustrative embodiment may be considered thatcontains 0.01% boronic acid, 0.3% initiator, 10% multivinyl monomer, andthe remainder is monovinyl monomer. In this embodiment, the monomers areall miscible with each other at the proportion used, and the remainingingredients are dissolved in the monomer mixture.

Preferably, in the organic solution, the sum of the weights of allmonomers, all initiators, all porogens, sulfur, and all boronic acidsis, by weight based on the weight of the organic solution, 75% to 100%;more preferably 90% to 100%, more preferably 95% to 100%; morepreferably 99% to 100%; more preferably 99.5% to 100%.

In porogen poor embodiments, preferably, the amount of monomer in theorganic solution, by weight based on the weight of the organic solution,is 90% or more; more preferably 95% or more; more preferably 98% ormore; more preferably 99% or more. Preferably, the amount of monomer inthe organic solution, by weight based on the weight of the organicsolution, is 99.9% or less.

The present invention involves an aqueous solution that contains PVOH.Preferably, the PVOH is dissolved in the aqueous solution. Preferably,the PVOH has degree of polymerization of 325 or higher; more preferably700 or higher; more preferably 900 or higher. Preferably, the PVOH hasdegree of polymerization of 5,000 or lower.

Preferably, PVOH has % hydrolyzed of 80% or more; more preferably 85% ormore. Preferably, PVOH has % hydrolyzed of 95% or less; more preferably90% or less.

Preferably the amount of PVOH is, by weight based on the weight of theaqueous solution, 0.01% or higher; more preferably 0.02% or higher; morepreferably 0.04% or higher. Preferably the total amount of PVOH is, byweight based on the weight of the water, 0.5% or less; more preferably0.2% or less; more preferably 0.1% or less.

The aqueous solution optionally contains one or more cellulosederivative dissolved in the aqueous solution. Among cellulosederivatives, preferred is carboxymethyl methylcellulose (CMMC). WhenCMMC is present, the preferred amount is, by weight based on the weightof the aqueous solution, 0.01% or more; more preferably 0.02% or more;more preferably 0.05% or more; more preferably 0.1% or more. When CMMCis present, the preferred amount is, by weight based on the weight ofthe aqueous solution, 1% or less; more preferably 0.5% or less; morepreferably 0.2% or less.

The aqueous solution preferably contains one or more nitrogen-containinginorganic salt dissolved in the aqueous solution. The inorganic salt hasa cation and an anion. Preferred cations are sodium, potassium, and amixture thereof; more preferred is sodium. Preferred anions are nitrite,nitrate, and a mixture thereof; more preferred is nitrite. The preferredamount of dissolved inorganic salt is, by weight based on the weight ofthe inorganic solution, 0.002% or higher; more preferably 0.005% orhigher; more preferably 0.01% or higher. The preferred amount ofdissolved inorganic salt is, by weight based on the weight of theinorganic solution, 0.2% or less; more preferably 0.1% or less; morepreferably 0.05% or less; more preferably 0.02% or less.

Preferably, the amount of water in the aqueous solution is, by weightbased on the weight of the aqueous solution, 90% or more; morepreferably 95% or more; more preferably 99% or more; more preferably99.5% or more. Preferably, the amount of water in the aqueous solutionis, by weight based on the weight of the aqueous solution, 99.99% orless.

In the practice of the present invention, the aqueous solution and theorganic solution are brought into contact with each other to form amixture. Preferably, the amount of organic solution, by weight based onthe weight of the mixture, is 10% or more; more preferably 15% or more;more preferably 20% or more. Preferably, the amount of organic solution,by weight based on the weight of the mixture, is 60% or less; morepreferably 50% or less; more preferably 40% or less; more preferably 30%or less.

Preferably, the mixture is subjected to mechanical agitation.Preferably, subsequent to the mechanical agitation, the mixture has theform of droplets distributed in an aqueous medium. The resultingcomposition, in which droplets are distributed in an aqueous medium, isknown herein as the suspension. Preferably, the volume fraction ofdroplets, based on the volume of the mixture, is 0.2 or more; morepreferably 0.25 or more; more preferably 0.30 or more; more preferably0.35 or more. Preferably, the volume fraction of droplets, based on thevolume of the mixture, is 0.55 or less; more preferably 0.50 or less;more preferably 0.45 or less.

The mechanical agitation may be performed by any apparatus. Suitablemethods of mechanical agitation include, for example, shaking, stirring,homogenizing, passing through a static mixer, jetting, and combinationsthereof. Preferred is jetting. Suitable jetting methods are described inU.S. Pat. No. 4,444,960 and U.S. Pat. No. 4,623,706.

The suitable and preferred ingredients and amounts for the droplets arethe same as those described above for the organic solution. Thecomposition of the droplets may not be exactly identical to thecomposition of the organic solution that was used in the process ofmaking the suspension.

The suitable and preferred ingredients and amounts for the aqueousmedium are the same as those described above for the aqueous solution.The composition of the aqueous medium may not be exactly identical tothe composition of the organic solution that was used in the process ofmaking the suspension.

Preferably, the harmonic mean size of the droplets is 100 μm or larger;more preferably 200 μm or larger; more preferably 300 μm or larger; morepreferably 400 μm or larger. Preferably, the harmonic mean size of thedroplets is 2,000 μm or smaller; more preferably 1,500 μm or smaller;more preferably 1,000 μm or smaller.

Gelatin may or may not be present in the suspension. When gelatin ispresent, the amount is, by weight based on the weight of the water, 2%or less; or 1% or less; or 0.5% or less. Preferred embodiments havelittle or no gelatin. Preferably the amount of gelatin is sufficientlylow that the amount of gelatin is, by weight based on the weight ofwater, 0 to 0.01%; more preferably 0 to 0.001%. More preferably theamount of gelatin is zero.

The suspension may or may not contain boric acid. When boric acid ispresent, the amount may be, by weight based on the weight of water, 2%or less, or 1% or less, or 0.5% or less. Preferably, the suspensioncontains little or no boric acid. Preferably, the amount of boric acidin the suspension is sufficiently low that the amount of boric acid is 0to 0.01% by weight, based on the weight of water; more preferably 0%.

The suspension may or may not contain chromium atoms in any valencestate.

Preferably, the suspension contains little or no chromium atoms.Preferably, the amount of chromium atoms in the suspension issufficiently low that the amount of chromium atoms is, by weight basedon the weight of the suspension, 0 to 0.01%, more preferably 0%.

A preferred use for the suspension is as the starting point for aprocess of suspension polymerization.

Polymerization conditions involve conditions in which the initiatorforms sufficient free radicals to initiate the polymerization process.For example, when a thermal initiator is used, polymerization conditionsinvolve establishing a temperature above 25° C. that is high enough fora significant fraction of the initiator molecules to decompose to formfree radicals. For another example, if a photoinitiator is used,polymerization conditions involve exposing the initiator to radiation ofsufficiently low wavelength and of sufficiently high intensity for asignificant fraction of the initiator molecules to decompose to formfree radicals. For another example, when the initiator is a redoxinitiator, polymerization conditions involve the presence ofsufficiently high concentration of both the oxidant and the reductantsuch that a significant number of free radicals are produced.Preferably, a thermal initiator is used. Preferably, polymerizationconditions involve temperature of 50° C. or higher; more preferably 65°C. or higher; more preferably 75° C. or higher. Preferably, when athermal initiator is used, the suspension is provided at a temperatureor a temperature range that falls within the range of 15° C. to 30° C.,and then the temperature is raised to polymerization conditions.

In conducting the polymerization process, various conditions, such as,for example, mechanical agitation, temperature, pH, or some combinationthereof, may be changed during the process.

Preferably, the polymerization process is a vinyl polymerizationprocess.

Preferably, polymerization takes place inside the droplets. Preferablythe polymerization process is a suspension polymerization process.

Preferably, the polymerization process results in a polymericcomposition.

Preferably, the polymeric composition contains polymeric particles.Polymeric particles are particles that are solid at 25° C. and thatcontain polymer in the amount, by weight based on the weight of thepolymeric particles, of 80% or more; preferably 90% or more; morepreferably 95% or more.

Preferably the polymeric particles have volume average particle size of100 μm to 1,500 μm.

Preferred polymers in the polymeric particles are the polymers formed byfree radical polymerization of the preferred monomers described above.Preferably the polymer contains polymerized units of vinyl monomer inthe amount, by weight based on the weight of the polymer, of 25% ormore; more preferably 50% or more; more preferably 75% or more; morepreferably 90% or more.

The present invention is not limited to any specific theory. Thefollowing discussion may serve to illustrate some of the ideas that maybe relevant to the present invention.

Once a distribution of droplet sizes is set in the suspension of organicdroplets in an aqueous medium, it is often desirable, and sometimesnecessary, to preserve this size distribution though a polymerizationprocess. This is particularly important in systems in which thesuspension droplet size distribution is very uniform, such as when thedroplets are formed by a jetting process.

The key attributes of an aqueous phase needed to preserve the suspensionsize distribution are 1) sufficient protection of the droplet surfacesto prevent direct organic-organic contact—and thus coalescence—betweendroplets and 2) sufficient interfacial energy and surfacecharacteristics to minimize the formation of ‘new’ surface—and thussheardown of a given droplet into smaller droplets—under a shear field.

For any given system, there is usually a balance between these twoattributes. Protection against coalescence usually improves as theconcentration of an aqueous soluble, protective polymer increases, asmore of the polymer goes to the surface of the droplets. This improvesprotection by providing more steric resistance to direct droplet-dropletcontact. But at the same time, an increased surface concentration ofprotective polymer tends to decrease interfacial energy, resulting inmore likelihood of sheardown.

Agitation system design can have an impact on this trade-off, as systemshaving maximum ‘flow’ (the more flow, the more ‘separated’ the dropletswill be, minimizing collision frequency and thus coalescence) andminimum shear (minimizing sheardown) are desirable. But there is apractical limit to this approach, as the agitation system hasrequirements other than size distribution (mainly heat transfer andproduct quality). For systems where preservation of a suspension sizedistribution (especially a uniform size distribution) is desirableand/or necessary, the chemistry needs to be optimized to the greatestdegree possible between minimizing both coalescence and sheardown.

Development of a surface ‘structure’ is one approach to attain thisoptimized balance. Formation of a ‘crosslinked’, or ‘complexed’ layeraround an entire droplet should improve protection vs. coalescencerelative to an uncrosslinked system of individual polymer chains at thedroplet surface—the mobility of polymer at a given location would berestricted by the network, leading to less likelihood of directdroplet-droplet contact. At the same time, if the network morphology issuch that the polymer is flexible (vs. rigid), it can be envisioned thatthe surface under a shear field would be more likely to deform than to‘break apart’.

Development of this type of polymer network is now known to occur viathe interaction of polyvinyl alcohol and boric acid/borate. Thischemistry, carried out in water, appears to result in precipitation of avery deformable, ‘sticky’ polymer phase. The approach of this inventionis to produce this type of polymer, but at the surface of a droplet andnot in the bulk aqueous phase. The means by which this has beenaccomplished is to add an organic soluble boronic acid to the organicphase. Some portion of the boronic acid would be expected to present atthe droplet interface, where crosslinking of PVOH can occur.

The following are examples of the present invention.

The following materials were used:

-   -   DI water=deionized water    -   CMMC=carboxymethyl methylcellulose    -   PVOH1=SelVol™ 523 polyvinylalcohol, 87 to 89% hydrolyzed, degree        of polymerization 1000 to 1500, from Sekisui Specialty Chemicals    -   PVOH2=SelVol™ 540 polyvinylalcohol, 87 to 89% hydrolyzed, degree        of polymerization 1600 to 2200, from Sekisui Specialty Chemicals    -   DVB=divinyl benzene (purity 63% by weight)    -   BPO=benzoyl peroxide (purity 75% by weight)    -   Styrene (purity >99%)    -   VPBA=4-vinylphenyl boronic acid

Interfacial Tension Test

Compositions were subjected to an interfacial tension test (IFT) asfollows.

Interfacial tension tests were performed with Kruss EasyDyne Model K20tensiometer (DuNuoy Ring Method). A dish of diameter at least twice thediameter of testing ring of the instrument was provided. A layer ofaqueous solution deep enough to fully cover the testing ring was placedin the dish, and the testing ring was lowered until it was barelysubmerged in the aqueous solution. Organic solution was slowly poured ontop of the aqueous solution to create a layer of organic solutionresting on top of the aqueous solution. The sample was allowed toequilibrate, and then the dish was lowered. The force needed to maintainthe position of the ring was used to measure the interfacial tension,which is reported in dynes per centimeter, or d/cm. Also, observationswere made of the behavior of the sample during the lowering of the dish.Categories of behaviors observed were as follows:

-   -   a) Normal: normal behavior for an IFT test; ring pulls through        the aqueous/organic interface and then the interface detaches        from the ring at some very short distance into the organic        layer. When the top surface of the organic layer has been        lowered below the ring, no structures are attached to the ring.    -   b) Membrane: As the dish was lowered, the interface between the        aqueous solution and the organic solution behaved like a        membrane that did not break. As the ring traveled through the        layer of organic solution, the apparent membrane remained        attached to the ring and draped over the ring to remain in        contact with the interface between the aqueous solution and the        organic solution. This continues even as the organic layer drops        below the ring level. The “IFT” value (the force exerted on the        ring) remained relatively low (reported as “IFT” in the table        below) as the ring traveled through the organic solution layer        and then jumped to a relatively high value when the ring passed        through the interface between the organic solution layer and air        (reported in the “observations” below as “air IFT”).    -   c) Skin: At the end of the test, as the dish was being lowered,        one or sometimes several strings could be seen adhered to the        ring. These strings, while very thin (estimate less than 100 μm)        can be as much as 3-4 cm in length. The strings sometimes extend        from the ring to the edge of the container holding the aqueous        and organic solutions. The presence of strings was almost always        seen when the ‘Membrane’ behavior was observed while the IFT        determination was in progress.    -   d) Precipitate: white precipitate formed in aqueous layer before        starting the test. In some cases, the ring did not pull through        the monomer layer.

The membrane/skin behavior is desirable, as it indicates a highly‘stretchable’, deformable surface that will be resistant to dropletcoalescence via a strongly adhered layer (or multi-layer) of highmolecular weight polymer. It is also anticipated that this behavior willlead to resistance to sheardown under stress—the droplet surface willstretch, as opposed to rupturing to form two or more smaller dropletsfrom one larger one.

PREPARATIVE EXAMPLE 1: ORGANIC SOLUTIONS

Organic solutions were prepared by combining the following ingredients:

Organic Solution Ingredients: Ingredient amount⁽¹⁾ Styrene balance⁽²⁾DVB 9.6% BPO 0.3% sulfur 0.0052 boronic acid variable Note: ⁽¹⁾% byweight based on the total weight of droplet ingredients. Note: ⁽²⁾tomake up 100% by weight

PREPARATIVE EXAMPLE 2: AQUEOUS SOLUTIONS

Aqueous solutions were prepared by combining the following ingredients:

Aqueous Solution Ingredients ingredient amount⁽³⁾ DI water balance⁽⁵⁾CMMC variable PVOH⁽⁴⁾ 0.06% NaNO₂ 0.016% Note: ⁽³⁾% by weight based onthe total weight of aqueous phase ingredients Note: ⁽⁴⁾either PVOH1 orPVOH2 Note: ⁽⁵⁾to make up 100% by weight

EXAMPLE 3: INTERFACIAL TENSION TESTING

The interface between a layer of organic solution and a layer of aqueoussolution was tested using the IFT procedure described above. It iscontemplated that a strong interface in this test would indicate thatthe same combination of aqueous solution and organic solution would forma good suspension of droplets of organic solution in aqueous solution.“Approx.” means approximately. The results were as follows:

Example % VPBA IFT (d/cm) Observations 3-2 0.0001 approx. 12 normal 3-30.001 approx. 12 normal 3-4 0.003 7.2 skin formed 3-5 0.005 6.7 membraneand skin; air IFT 46.8 d/cm 3-6 0.0075 4.8 membrane and skin; air IFT41.9 d/cm 3-7 0.01 4.9 membrane and skin; air IFT approx. 48 d/cmFurther IFT test results were as follows:

Example % VPBA IFT (d/cm) Observations 3-8 0.015 6.5 membrane and skin;air IFT 45.3 d/cm 3-9 0.02 10.5 precipitate; ring did not pull throughthe monomer layer 3-10 0.025 11.3 precipitate; ring did not pull throughthe monomer layer 3-11 0.03 11.4 precipitate; ring did not pull throughthe monomer layer 3-12 0.05 12.2 precipitate 3-13 0.1 10.2 precipitate

Examples 3-2 and 3-3 showed that with too little amount of boronic acid,the desired strengthening of the interface does not occur. All the otherexamples showed useful behavior, at least initially. Examples 3-4through 3-11 showed especially desirable behavior, with the interfacebetween the organic solution and the aqueous solution forming a verystrong membrane-like layer.

EXAMPLE 4: PREPARATION OF SUSPENSIONS WITHOUT CMMC

During the preparation of the suspension, some individual ingredients orpartial mixtures were, if necessary, temporarily heated to achieve goodmixing, but the suspension was provided at approximately 25° C.

Using the organic and aqueous solutions described in Examples 1 and 2,suspensions of droplets of organic solution suspended in a medium ofaqueous solution were made using the jetting procedure described in U.S.Pat. No. 4,444,960 and U.S. Pat. No. 4,623,706. This procedureconsistently produces droplets with volume-average diameter of 480 μmand uniformity coefficient less than 1.1. In the resulting suspension,the volume fraction of droplets of organic solution was 0.4.

A thin layer of each suspension was placed on a glass slide and examinedby optical microscopy to produce a photomicrograph. The photomicrographswere manually examined. The droplets of diameter of approximately 400 μmto 600 μm (“normal” droplets) were counted, as were the droplets havingdiameter less than approximately 250 μm (“small” droplets). The numberof small droplets per 100 normal droplets is reported herein as the“small count”. No CMMC was used. PVOH type was PVOH1. “Ex.” meansExample. Examples with designation ending in “C” are comparative.Results were as follows:

Example % VPBA Diameter⁽¹⁾ (μm) Small Count 4-1C 0 480 118 4-2 0.01 4803 Note: ⁽¹⁾volume-average diameter, known from the consistent results ofthe jetting procedure.As the small count shows, Example 5-2 has a far more uniformdistribution of droplet sizes than Comparative Example 5-1C.

EXAMPLE 5: SUSPENSIONS WITH CMMC

During the preparation of the suspension, some individual ingredients orpartial mixtures were, if necessary, temporarily heated to achieve goodmixing, but the suspension was provided at approximately 25° C.

Using the organic and aqueous solutions described in Examples 1 and 2,suspensions of droplets of organic solution suspended in a medium ofaqueous solution were made using the jetting procedure described in U.S.Pat. No. 4,444,960 and U.S. Pat. No. 4,623,706. In the resultingsuspension, the volume fraction of droplets of organic solution was 0.4.

Monomer droplet size was volume-average diameter of 480 μm, resultingfrom the jetting procedure.

Jetting was performed at approximately 25° C., and the suspension washeld with stirring for approximately 20 hours. Then the temperature wasraised to 80° C. and held at a temperature between 80° C. and 100° C.for 10 hours, and then the composition was cooled to approximately 25°C. The composition underwent a process of suspension polymerization,converting the monomer droplets to polymer particles.

Size of the polymer particles was analyzed by performing opticalmicroscopy to form digital images of the particles, then performingimage analysis to determine the diameter of each particle, and thencalculating the desired statistics from the data base of observeddiameters. Results were as follows:

PVOH Ex % VPBA % CMMC type HMS (μm) UC LT355 5-1 0.01 0.15 PVOH2 4681.06 1.66 5-2 0.01 0.15 PVOH2 466 1.06 3.45 5-3 0.01 0.15 PVOH2 477 1.070.41 5-4 0.0025 0.15 PVOH2 469 1.11 4.35 5-5C 0 0.23 PVOH1 443 1.7 15.65-6C 0 0.23 PVOH1 407 1.37 12.2Examples 5-1, 5-2, and 5-3 are replicate samples. Also, Examples 5-5Cand 5-6C are duplicate samples. All of the inventive examples 5-1through 5-4 have much more uniform particle size distributions (i.e.,smaller values of UC and lower values of LT355) than the comparativeexamples 5-5C and 5-6C. The difference in uniformity between theinventive examples and the comparative examples is considered to beextremely significant; at a production scale, this difference could meanthat the inventive process was economically viable while the comparativeprocess was prohibitively expensive.

1. A composition comprising droplets distributed in an aqueous medium,wherein the droplets comprise one or more boronic acids, and wherein theaqueous medium comprises polyvinyl alcohol.
 2. The composition of claim1, wherein the one or more boronic acids are present in an amount of0.0015% to 0.03% by weight based on the weight of the droplets.
 3. Thecomposition of claim 1, wherein the polyvinyl alcohol is present in anamount of 0.01% to 0.5% by weight based on the weight of the aqueousmedium.
 4. The composition of claim 1, wherein the droplets additionallycomprise one or more monomers and one or more initiators.
 5. Thecomposition of claim 1, wherein the droplets additionally comprise oneor more monomers and one or more initiators, and wherein the one or moremonomers are present in an amount of 95% to 99.99% by weight based onthe weight of the droplets.
 6. The composition of claim 1, wherein thedroplets additionally comprises one or more porogens, and wherein theone or more porogens are present in an amount of 10% to 60% by weightbased on the weight of the droplets.